Production of photographs in blue-black tones and compositions thereof



I ing blue-black toning agents.

- benzimidazole, and-the like, have been employed for this purpose. These compounds, however,

. photographic developer.

Patented May 15 1351 UNITED STATES PATENT oFFlc-E v I, f. P'PRODUCTION OF PHOTOGRAPHS IN BLUE-BLACK 'IONES AND COMPOSI- TION S THEREOF Harold o. Harsh, Binghamton, N. Y., assignor to "General Aniline & Corporation, New

. York, N. Y., a corporation of Delaware No Drawing. Application August 1, 1946, I Serial N0. 687,713 g,

1 g 4 This invention relates to a photographic process for producing blue-black tones in silver images, to photographic elements, and to photographic developer and treating solutions contain-- Various organic compounds for the production of photographs from silver-halide emulsions in b1ue;black tones have been suggested; from time to time. Thus, for example, benzotriazole, nitrohave the disadvantage-t gradually decomposing in the developer as a result of which they considerably retard development. Moreover, these compounds are very sensitive to oxidizing and reducing agents usually employedin photographic developersso that then blue-black toning eiiect of the "developer very rapidly diminishes and after a time ceases altogether.

In accordance with the present invention,

blue-black shades ortones, are obtained while avoiding all of the aforementioned shortcomings and disadvantages of the prior proposals.

An object ofthe present invention is toprovide a process for the production of blue-black tones in vere alideemuls o A"further object is toprovide a newcla'ssof blue-black toning agents which are added to a and wherein R and R1 are hydrogen, lower alkyl, e. 3.,

8Claims. on. -88) r z the like, 5- or 6-membered alicyclic ring structure, e. g., cyclopentyl cyclohexyl, and the like, aryl, e. g., phenyLna'phthyl, diphenyl, etc., or a 5- or 6-membered heterocyclic radical containing not more than two hetero atoms, e. g., pyridyl,

furyl, pyrryl, pyrazolyl, and the like, R2 is amino, hydroxy,carbalkoxy, e. g, carhomethoxy, carbethoxy, carbpropoxy, and the like, or an alkyl,

aryl, alicyclic, or heterocyclic, radical of the same value as R, Y is an amino or hydroxy group, and Z represents the atoms necessary to complete either a five-memberedor 'six-mer'nbered alicyclic or heterocyclic ring structure of the same value as iven for R.

Typical compounds corresponding to the foregoing general formula which are included in this invention,are'as follows? l 2 i l 0H CH3- 1 7-hydroxy-5methyl-1,3,4-triazaindolizine 1;

7-hydroxy 6-ethy1-5-methy1 1;3,4-triazaindolizine 7-hydrox'y et hyl-2',o diinthyl i,3g4 triazbiindolizine (4) OH: I 1

amass sting-atria1-i;s;i:eiiziisat1site Q g a act-spoof 8-amino 2-a-furyl-cyclopentano [f] "fi,3,4] triazaindolizine l l CHEF 7-.aminoeii methyldfiAiriazaindolizine NHa 7-amino fi-pheny1-1,3,4-triazaindolizine N 7-amino-5-methy1-2-pheny1-1,3,4=triazaindolizine Merino S-metHyLepmnyLI,warrazaiidonime IITH:

'Q-(LN/LN v v 7-amino-5-B-py1idy1 1 ,SKti-ieiZaindolizine all C CH;

Hg- C 3 7-amino-2-cyc1oheiFI-5anethYi-1,SA-tfiidzaindolizine CHa- =N N w 7-amino-6-B-pynidy1-1;i i triazaindolizine orb-om noo ls-N om-og \CE onro .,=N

I "N 7-amino-5-methy1-6-cyc10hexy1-1,3,4-triazaindolizine The n ethod for the preparation of the .hydroxy-1,3,4-triazaindo1izines illustrated by compounds 1 to 19 is given in the literature. The

method consists of heating -1 mol of a fi-ket'ri ester, a malonic ester, or .a mononitrile of a malonic ester, with 1 mol zof a 3-amino-1,2,4- triazole of the following general formula:

RFO/ im' reaction conditions as given the above references. The method for the preparation of the product of the type illustrated by compound 11 consists of heating 1 mol of a mononitrile of a malonic ester with 1 mol of a" 3-amino-1,2,4- triazole. V v

The method -forwthe prepamation" of the hy- The same condi' droxy-I,3,4 triazaindolizines, illustrated by compounds 20 to 46, inclusive, by condensing a p-keto ester with a 3-amino-1,2,4-triazole is given in the aforementioned references. By substituting a cyclic B-keto ester'or nitrile, a p-imino nitrile, or a p-keto nitril for the s-keto ester and employing the same reaction conditions described in these references, the aminoand hydroxy-1,3,4- triazaindolizines utilized in accordance with this invention are readily prepared. The blue-black toning agents of the present invention are preferably used in developing solutions in which they diffuse to the exposed silver halide grains and produce a blue-black toning efiect during the course of development.

The degree of blue-black tones obtained upon development varies somewhat with the silverhalide ratio of the emulsion used in coating the film, plate, or paper support containing the toning agents. Optimum results, i. e., most pleasant blue-blacktones, are obtained with silver chloride emulsions where the ratio of silver bromide to silver chloride by weight is less than 1 to 40. With silver-halide emulsions, which are especially prepared to give colder tones, the photographic material, 1. e., film, plate, or paper, containing the toning agents, blue-black toning effects are still obtained where the ratio of silver bromide to silver chloride is 1 to 2. These silverhalide emulsions may also carry silver iodide up to one part of silver iodide by weight to 20 parts of the silver bromide and silver chloride combined.

The concentration of the particular toning agent in developing solutions may vary from 20 mg. to 100 mg. per liter. The most desirable concentration, however, can be readily determined by conducting a few simple experiments.

The invention will be further illustrated, but is not intended to be limited, by the following examples.

Example I Ametol-hydroquinone developer of the following composition was prepared:

Hot water (125 F. or 52 C.) cc 750 p-Monomethyl-amine-m-phenol sulfate grams 3.5 Sodium sulfite (anhydrous) Q do.. 45 Hydroquinone do 11.5 Sodium carbonate (monohydrate) do '78 Potassium bromide do 1.2 Water to make "liter-.. 1

To this developer solution,i60- mgs. of 'Z-amino- 5-methyl-1,3,4-triazaindolizine were added. Upon development of an exposed gelatino silverhalide emulsion, containing silver bromide and silver chloride in the ratioof 1 to 40, respectively, blue-black tones were produced in the silver im- Eacample II I ,Example 1. was repeated withthe exception that an equivalent quantity,of 'T-hydroxy-5- lfl-pyridyl]-1,3,4-triazaindolizirie was substituted for 7-amino-5-methyl-1,3,4-triazaindolizine.

It will be apparent that the amounts of the foregoing toning agents may vary with the different types of photographic and developing compositions. The optimum quantities, however, required vfor a particular composition can be readily determined bya few simple tests. After exposure, developing, fixing, and. drying, the image obtained. is .of. a. blue-black color instead of.

1-0 the brownish-black or black obtained "with an untreated element. "f

While I have, in this specification, specifically described several embodiments which my invention may assume in practice, it will be further understood that the same are shown for purposes of illustration only and that the invention may be further modified and embodied in various other forms without'departing from the spirit or scope of the appended claims. 1

I claim:

'1. The process for producing developed silver pictures in blue-blacktones which comprises developing an exposed light-sensitive silver-halide emulsion layer; with an aqueous solution of an alkaline photographic developer for silver halide emulsions comprising anaromatic silver halide developing agent, said solution containing from 20 to mgs. per liter of said developer 2. 1,3,4-triazaindoliaine selected from the classco nsieflting of those corresponding to the generalform ae: l

and

wherein R and R1; are members selected fromthe class consisting of hydrogen, lower alkylfaryl, an alicyclic ring structure of from 5 to ficarbon atoms, and a heterocyclic. group of from 5 to 6 members containing not more than two hetero atoms. R2 is a member selected from the class" consisting of amino, hydroxy, alkyl, carbalkoxy," aryl, and alicyclic ring structure-of from 5 to 6; carbon atoms, and a heterocyclic group of from 5 to 6 members containing not more than two hetero atoms, Y is a member selected from the class consisting of amino and hydroxy, and Z represents the atoms necessary to complete a member selected from the class consisting of a S-membered and fi-mernbered alicyclic ring structure and a B-membered and G-membered heterocyclic ring structure containing not merge than two hetero atoms.

2. The process for producing developed silver pictures in blue-black tones which comprises de veloping an exposed light-sensitive silver halide emulsion layer with an aqueous solution of an alkaline photographic developer for silver halide emulsions comprising'an aromatic silver halide developing agent, said solution containing from 20 to- 100 mgsrper liter of-"said developer a 1,3,41- triazaindolizine corresponding to theformula:

3. ,The process" for:v producing, developed silver pictures in blue-black tones which: comprises developing an; exposed light sensitive silverhalide. emulsion. layer with an aqueous solution oi analkaline photographicv developer for silver halide emulsions comprising an aromatic silver halide I developing agent, said solution containing from 20 to 100 mgs. per liter of said developer a 1',3',4-.-triazaindolizine corresponding to the for.- mula:

4.. The process for producing developed silverpictures in blue-black tones which comprises. developing an exposed light-sensitive silver-halide emulsion layer with an aqueous solution of an alkaline photographic developer for silver halide emulsions comprising an aromatic silver halide developing agent, said'solution containing from 20 to 100 mgs. per liter of said developer a 1,3,4- triazaindolizine corresponding to the formula:

o N N l CH o=o o =N 5. A photographic developer for development of exposed lights-sensitive silver-halide emulsions consistingof an aqueous solution. of. an alkaline photographic developer for silver halide emulsions comprising an aromatic silver halide developing agent, said solution containing from20 to l mgsl per-liter of said developer a 1,3,4- triazaindolizine selected from the class. consisting ofr-those corresponding to the generalformulae:

and

are members selected from,

two hetero atoms; Y is a'memberselected from the class consisting of amino and. hydroxy, and Z represents the atoms necessary to complete a member selected from the class consisting of a S-membered and fi-membered alicyclic ring structure and a 5-membered and fi-membered heterocyclic ring structure containing not more than two hetero atoms.

6. A. photographic developer for development of exposed light-sensitivesilver-halide emulsions consisting of an. aqueous solution of an' alkaline photographic developer for silver halide emul-' sions comprising an aromatic silver halide developingagent, said solutioncontaining from 20 to mgs. per liter of said developer a 1,3,4- triazaindolizine of the formula:

8. A photographic developer for development of exposed light-sensitive silver-halide emulsions consisting of an aqueous solution of an alkaline photographic developer for silver halide emulsions comprising anaromatic silver halide developing agent, said solution containing from 20 to 100 mgs. per liter of said developer a 1,3,4- triazaindolizine of the formula:

HAROLD C. HARSH.

REFERENCES CITED The following references are of record in the "file of this patent:

UNITED STATES PATENTS Number Name Date 1,693,500 Wheeler Nov. 2'7, 1928 2,158,184 Heckman et al. May 16, 1939 2,390,707 I-leimbach Dec. 11, 1945 2,432,419 Heimbach Dec. 9, 1947 2,444,605 Heimbach .4 July 6, 1948 2,444,606 I-Ieimbach July 6, 1948 2,444,607: Heimbach --July 6. 1948- 

1. THE PROCESS FOR PRODUCING DEVELOPED SILVER PICTURES IN BLUE-BLACK TONES WHICH COMPRISES DEVELOPING AN EXPOSED LIGHT-SENSITIVE SILVER-HALIDE EMULSION LAYER, WITH AN AQUEOUS SOLUTION OF AN ALKALINE PHOTOGRAPHIC DEVELOPER FOR SILVER HALIDE AMULSIONS COMPRISING AN AROMATIC SILVER HALIDE DEVELOPING AGENT, SAID SOLUTION CONTAINING FROM 20 TO 100 MGS. PER LITER OF SAID DEVELOPER A 1,34-TRIAZAINDOLIZINE SELECTED FROM THE CLASS CONSISTING OF THOSE CORRESPONDING TO THE GENERAL FORMULAE: 